Solid dielectric capacitor and method of manufacture

ABSTRACT

A monolithic capacitor having a dielectric ceramic body cosintered with at least two base metal electrodes. The ceramic body is composed of a major ingredient expressed by the formula, 
     
         (1-α) {(Ba.sub.k-x M.sub.x)O.sub.k (Ti.sub.1-y R.sub.y)O.sub.2-(y/2) 
    
      }+αCaZrO 3   
     where M is either or both of calcium and strontium, R is a rare earth element or elements, and α, k, x and y are numerals in specified ranges. To this major ingredient is added a minor proportion of an additive. The additive is a mixture of boric oxide or lithium oxide, silicon dioxide and at least one metal oxide selected from among barium oxide, strontium oxide, calcium oxide, magnesium oxide and zinc oxide. For the fabrication of capacitors the mixture of the above major ingredient and additives in finely divided form are formed into moldings of desired shape and size, each with at least two electrodes buried therein. The moldings and electrodes are cosintered in a reductive or neutral atmosphere at temperatures of less than 1200 degrees C. and then are heated at a lower temperature in an oxidative atmosphere.

BACKGROUND OF THE INVENTION

Our invention relates to solid dielectric capacitors and more particularly to a monolithic ceramic capacitor comprising a single or multiple layered ceramic body and at least two electrodes in contact therewith. The invention also pertains to a method of fabrication such capacitors.

Multilayered ceramic capacitors have long been known and used extensively which employ noble metals such as platinum and palladium as the electrode materials. Generally, for the fabrication of such capacitors, "green" (unsintered) dielectric sheets have first been prepared from the proportioned ingredients of a desired dielectric ceramic material in finely divided form. An electroconductive paste containing powdered platinum or palladium has then been "printed" on the green sheets in a desired pattern. Then a plurality of such printed green sheets have been stacked up, pressed together, and sintered in a temperature range of 1300 degrees to 1600 degrees C. in an oxidative atmosphere.

This conventional method makes possible the simultaneous firing (cosintering) of the dielectric ceramic layers and the film electrodes interleaved therewith. It is also an acknowledged advantage of this known method that the noble metal electrodes are totally unaffected by the high temperature sintering in an oxidative atmosphere. Offsetting all such advantages is the expensiveness of the noble metals, which add substantially to the manufacturing costs of the multilayered ceramic capacitors.

Wada et al. U.S. Pat. No. 4,610,969, assigned to the assignee of the instant application, suggests a solution to the above problem. It teaches dielectric ceramic compositions consisting of a major ingredient expressed by the formula, (Ba_(k-x) M_(x))O_(k) TiO₂, where M is at least either of magnesium (Mg) and zinc (Zn), and additives consisting of lithium oxide (Li₂ O) and silicon dioxide (SiO₂). The compositions may, or may not, additionally include at least one metal oxide selected from among barium oxide (BaO), calcium oxide (CaO) and strontium oxide (SrO).

Another solution is found in Wada et al. U.S. Pat. No. 4,610,970, which proposes ceramic compositions whose major ingredient is expressed by the formula, (Ba_(k-x-y) M_(x) L_(y))O_(k) TiO₂, where M is at least either of Mg and Zn, and L is at least either of Sr and Ca. To this major ingredient are added Li₂ O, SiO₂ and, optionally, at least one other metal oxide selected from among BaO, CaO and SrO.

Wada et al. U.S. Pat. No. 4,610,971 suggests still another solution, teaching use of a major ingredient expressed by the formula, (Ba_(k-x) M_(x))O_(x) TiO₂, where M is at least one of Mg, Zn, Sr and Ca. This major ingredient is admixed with boric oxide (B₂ O₃), SiO₂ and, optionally, at least one other metal oxide selected from among BaO, MgO, ZnO, SrO and CaO.

A further solution is found in Wada et al. U.S. Pat. No. 4,610,968, which proposes ceramic compositions including a major ingredient expressed by the formula, (Ba_(k-x) M_(x))O_(x) TiO₂, where M is at least one of Mg, Zn, Sr and Ca. This major ingredient is admixed with B₂ O₃ and at least one metal oxide selected from among BaO, MgO, ZnO, SrO and CaO.

All the foregoing known compositions make possible the fabrication of ceramic bodies by firing at temperatures of not more than 1200 degrees C. in a nonoxidative (reductive or neutral) atmosphere. The ceramic bodies may therefore be cosintered with electrodes of a base metal such as nickel. The resulting capacitors have specific dielectric constants of not less than 2000, and the temperature dependences of their capacitances are within plus or minus 10 percent in a temperature range of -25 degrees to +85 degrees C.

While these values are satisfactory for all practical purposes, we have nevertheless been hard pressed by our customers, with the recent development of microelectronics, for ceramic capacitors that have higher specific dielectric constants with no less temperature dependences.

SUMMARY OF THE INVENTION

We have hereby invented how to manufacture ceramic capacitors that have higher dielectric constants, with less temperature dependences over a wide temperature range, than heretofore and which can be formed by firing in a temperature range of not more than 1200 degrees C. in a nonoxidative atmosphere.

Briefly stated in one aspect thereof, our invention provides a solid dielectric capacitor of the above improved characteristics, comprising a low temperature sintered dielectric ceramic body and at least two electrodes in contact therewith. The ceramic body consists essentially of 100 parts by weight of a major ingredient that is expressed by the formula, (1-α){(Ba_(k-x) M_(x))O_(k) (Ti_(1-y) R_(y))O₂₋(y/2) }+αCaZrO₃, and 0.2 to 5.0 parts by weight of an additive mixture (hereinafter referred to as the additive ingredient) of at least two members selected from the group consisting of B₂ O₃ or Li₂ O, SiO₂ and at least one of BaO, SrO, CaO, MgO and ZnO. In the formula of the major ingredient, M is either or both of calcium(Ca) and strontium(Sr), R is at least one metal selected from scandium(Sc), yttrium(Y), gadolinium(Gd), dysprosium(Dy), holmium(Ho), erbium(Er), ytterbium(Yb), terbium(Tb), thulium(Tm) and lutetium(Lu), α is a numeral in the range of 0.005 to 0.040, k is a numeral not less than 1.00 and not more than 1.05, x is a numeral in the range of 0.005 to 0.05, and y is a numeral greater than 0 and not greater than 0.04. The relative proportions of B₂ O₃ or Li₂ O, SiO₂ and at least one selected metal oxide, altogether constituting the additive mixture, will be specified with reference to the ternary diagrams attached hereto.

Another aspect of our invention concerns a method of fabricating the ceramic capacitor having the ceramic body of the above specified composition. The method dictates, first of all, the preparation of a mixture of the above specified major ingredient and additives in finely divided form. This mixture is then molded into a body of desired shape and size, which is provided with at least two electrode portions of an electroconductive material in any convenient manner. Then the moldings with the electrode portions are cosintered in a reductive or neutral atmosphere and is subsequently heated in an oxidative atmosphere.

The dielectric ceramic composition of our invention, set forth in the foregoing, makes it possible to sinter the moldings in a nonoxidative atmosphere at temperatures not exceeding 1200 degrees C. A preferred temperature range for this molding operation is from 1050 degrees to 1200 degrees C. The sintering temperatures of less than 1200 degrees C. enable the use of nickel or like low cost base metal as the electrode material in cosintering the ceramic boy and the electrodes.

Therefore, in the fabrication of ceramic capacitors by the method of our invention, an electroconductive paste of powdered nickel or like base metal may be printed, coated, or otherwise formed on green sheets of the dielectric ceramic compositions in accordance with our invention. The green sheets and the electroconductive layers thereon may be cosintered at temperatures of not more than 1200 degrees C.

The ceramic capacitors of our invention have proved to have very favorable physical and performance characteristics. The test capacitors manufactured in accordance with our invention, to be disclosed subsequently, had specific dielectric constants of more than 3000, dielectric losses of not more than 2.5%, and resistivities of not less than 1×10⁶ megohm-centimeters. Also the temperature dependences of their specific dielectric constants were from -15% to +15% of the value at 25 degrees C. in a temperature range of -55 degrees to +125 degrees C., and from -10% to +10% of the value at 20 degrees C. in a temperature range of -25 degrees to +85 degrees C.

The above and other features and advantages of our invention and the manner of realizing them will become more apparent, and the invention itself will be be understood, from a study of the following description and appended claims taken together with the attached drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a section through a monolithic, multilayered ceramic capacitor capable of fabrication in accordance with the teaching of our invention, the illustrated capacitor being representative of numerous test capacitors manufactured in the Examples of our invention to be presented subsequently;

FIG. 2 is a ternary diagram depicting the relative proportions of the second additives of the ceramic compositions in accordance with Examples 1-131 of our invention; and

FIG. 3 is a ternary diagram depicting the relative proportions of the second additives of the ceramic compositions in accordance with Examples 132-162 of our invention.

DETAILED DESCRIPTION

We have illustrated in FIG. 1 one of many monolithic ceramic capacitors of like construction fabricated in the subsequent Examples of our invention by way of a preferable embodiment thereof. Generally designated 10, the representative capacitor is shown to have an interlamination of three dielectric ceramic layers 12 and two film electrodes 14. The three ceramic layers 12 constitute in combination a solid dielectric body 15 having the low temperature sinterable ceramic compositions in accordance with our invention. The two film electrodes 14, which can be of a low cost base metal such as nickel, extend from both sides of the dielectric body 15 toward, and terminate short of, the opposite sides of the dielectric body and so have an overlapping, parallel spaced relation to each other.

The capacitor 10 also includes a pair of conductive terminations 16 which are formed on both sides of the dielectric body 15 and which contact the respective film electrodes 14. Each termination 16 is shown to comprise a baked on zinc layer 18, a plated on copper layer 20, and a plated on solder layer 22.

Typically, and as fabricated in the subsequent Examples of our invention, the intermediate one of the three dielectric layers 12 has a thickness of 0.02 millimeter (mm). The area of that part of each film electrode 14 which overlaps the other film electrode is 25 mm² (5×5 mm).

EXAMPLES

We fabricated 162 different sets of test capacitors, each constructed as shown in FIG. 1, some having their dielectric bodies formulated in accordance with the ceramic compositions of our invention and others not. Then we measured the specific dielectric constant, dielectric loss, resistivity, and temperature dependence of capacitance of the test capacitors. Tables 1, 2 and 3 list the compositions of the dielectric bodies of all the test capacitors fabricated.

We have previously defined the major ingredient of the ceramic compositions in accordance with our invention by the general formula,

    (1-α){(Ba.sub.k-x M.sub.x)O.sub.k (Ti.sub.1-y R.sub.y)O.sub.2-(y/2) }+αCaZrO.sub.3.

Thus, in Table 1, we have given various combinations of (1-α), α, (k-x), and x in the formula to indicate the specific major ingredients employed in the various Tests. The (1-α) and α indicate the relative proportions of (Ba_(k-x) M_(x))O_(k) (Ti_(1-y) R_(y))O₂₋(y/2) and CaZrO₃ of the major ingredient in moles. The (k-x) and x indicate the atomicities of the associated elements. Since M can be either or both of Ca and Sr, the column under X is subdivided into the atomicities of these elements and their sum (X).

In Table 2, we have given various combinations of y and k in the formula to indicate the specific majior ingredients employed in the various Tests. Since R is at least one metal selected from Sc, Y, Gd, Dy, Ho, Er and Yb, the column under y is subdivided into the atomicities of these elements and their sum(y). The k indicates the atmicity of the element (O).

The ceramic compositions of our invention also include an additive ingredient or glass ingredient. The additive ingredient is an additive mixture of B₂ O₃, SiO₂ and MO or an additive mixture of Li₂ O, SiO₂ and MO. Table 3 specifies the proportions, in parts by weight, of the additive ingredient with respect to 100 parts by weight of the major ingredient. Also, Table 3 specifies the relative proportions, in mole percent, of the additive ingredients B₂ O₃, Li₂ O, SiO₂, and MO. Further, since MO can be anyone or more of BaO, MgO, ZnO, SrO and CaO, Table 3 gives the relative proportions, in mole percent, of these metal oxides. In the Table 3, the additives of Tests Nos. 1-131 consist of Li₂ O, SiO₂ and MO, and the additive of Tests Nos. 132-162 consist of B₂ O₃, SiO₂ and MO.

                  TABLE 1                                                          ______________________________________                                         Caramic Compositions                                                           Major Ingredient                                                               (100 wt. parts)                                                                Test                    X                                                      No.    1 - α                                                                            α  k-x   Ca    Sr    Sum                                  ______________________________________                                         1      0.98    0.02     0.98  0.03  0.01  0.04                                 2      0.98    0.02     0.98  0.03  0.01  0.04                                 3      0.98    0.02     0.98  0.03  0.01  0.04                                 4      0.98    0.02     0.98  0.03  0.01  0.04                                 5      0.98    0.02     0.98  0.03  0.01  0.04                                 6      0.98    0.02     0.98  0.03  0.01  0.04                                 7      0.98    0.02     0.98  0.03  0.01  0.04                                 8      0.98    0.02     0.98  0.03  0.01  0.04                                 9      0.98    0.02     0.98  0.03  0.01  0.04                                 10     0.98    0.02     0.98  0.03  0.01  0.04                                 11     0.98    0.02     0.98  0.03  0.01  0.04                                 12     0.98    0.02     0.98  0.03  0.01  0.04                                 13     0.98    0.02     0.98  0.03  0.01  0.04                                 14     0.98    0.02     0.98  0.03  0.01  0.04                                 15     0.98    0.02     0.98  0.03  0.01  0.04                                 16     0.98    0.02     0.98  0.03  0.01  0.04                                 17     0.98    0.02     0.98  0.03  0.01  0.04                                 18     0.98    0.02     0.98  0.03  0.01  0.04                                 19     0.98    0.02     0.98  0.03  0.01  0.04                                 20     0.98    0.02     0.98  0.03  0.01  0.04                                 21     0.98    0.02     0.98  0.03  0.01  0.04                                 22     0.98    0.02     0.98  0.03  0.01  0.04                                 23     0.98    0.02     0.98  0.03  0.01  0.04                                 24     0.98    0.02     0.98  0.03  0.01  0.04                                 25     0.98    0.02     0.98  0.03  0.01  0.04                                 26     0.98    0.02     0.98  0.03  0.01  0.04                                 27     0.98    0.02     0.98  0.03  0.01  0.04                                 28     0.98    0.02     0.98  0.03  0.01  0.04                                 29     0.98    0.02     0.98  0.03  0.01  0.04                                 30     0.98    0.02     0.98  0.03  0.01  0.04                                 31     0.98    0.02     0.98  0.03  0.01  0.04                                 32     0.98    0.02     0.98  0.03  0.01  0.04                                 33     0.98    0.02     0.98  0.03  0.01  0.04                                 34     0.98    0.02     0.98  0.03  0.01  0.04                                 35     0.98    0.02     0.98  0.03  0.01  0.04                                 36     0.98    0.02     0.98  0.03  0.01  0.04                                 37     0.98    0.02     0.98  0.03  0.01  0.04                                 38     0.98    0.02     0.98  0.03  0.01  0.04                                 39     0.98    0.02     0.98  0.03  0.01  0.04                                 40     0.98    0.02     0.98  0.03  0.01  0.04                                 41     0.98    0.23     0.98  0.03  0.01  0.04                                 42     0.98    0.02     0.96  0.03  0.01  0.04                                 43     0.98    0.02     0.98  0.03  0.01  0.04                                 44     0.98    0.02     0.98  0.03  0.01  0.04                                 45     0.98    0.02     0.98  0.03  0.01  0.04                                 46     0.98    0.02     0.98  0.03  0.01  0.04                                 47     0.98    0.02     0.98  0.03  0.01  0.04                                 48     0.995   0.005    1     0.03  0.01  0.04                                 49     0.995   0.005    1     0.03  0.01  0.04                                 50     0.995   0.005    1     0.03  0.01  0.04                                 51     0.995   0.005    1     0.03  0.01  0.04                                 52     0.995   0.005    1     0.03  0.01  0.04                                 53     0.995   0.005    1     0.03  0.01  0.04                                 54     0.96    0.04     1     0.02  0.02  0.04                                 55     0.96    0.04     1     0.02  0.02  0.04                                 56     0.96    0.04     1     0.02  0.02  0.04                                 57     0.96    0.04     1     0.02  0.02  0.04                                 58     0.96    0.04     1     0.02  0.02  0.04                                 59     0.96    0.04     1     0.02  0.02  0.04                                 60     0.96    0.04     1     0.02  0.02  0.04                                 61     0.96    0.04     1     0.02  0.02  0.04                                 62     0.96    0.04     1     0.02  0.02  0.04                                 63     0.96    0.04     1     0.02  0.02  0.04                                 64     0.96    0.04     1     0.02  0.02  0.04                                 65     0.96    0.04     1     0.02  0.02  0.04                                 66     0.96    0.04     1     0.02  0.02  0.04                                 67     0.96    0.04     1     0.02  0.02  0.04                                 68     0.96    0.04     1     0.02  0.02  0.04                                 69     0.96    0.04     1     0.02  0.02  0.04                                 70     0.96    0.04     1     0.02  0.02  0.04                                 71     0.96    0.04     1     0.02  0.02  0.04                                 72     0.96    0.04     1     0.02  0.02  0.04                                 73     0.96    0.04     1     0.02  0.02  0.04                                 74     0.96    0.04     1     0.02  0.02  0.04                                 75     0.96    0.04     1     0.02  0.02  0.04                                 76     0.96    0.04     1     0.02  0.02  0.04                                 77     0.96    0.04     1     0.02  0.02  0.04                                 78     1       0        0.96  0.025 0.025 0.05                                 79     0.995   0.005    0.96  0.025 0.025 0.05                                 80     0.98    0.02     0.96  0.025 0.025 0.05                                 81     0.96    0.04     0.96  0.025 0.025 0.05                                 82     0.95    0.05     0.96  0.025 0.025 0.05                                 83     1       0        1     0.01  0.03  0.04                                 84     0.995   0.005    1     0.01  0.03  0.04                                 85     0.98    0.02     1     0.01  0.03  0.04                                 86     0.96    0.04     1     0.01  0.03  0.04                                 87     0.95    0.05     1     0.01  0.03  0.04                                 88     0.98    0.02     1     0     0     0                                    89     0.98    0.02     0.995 0.005 0     0.005                                90     0.98    0.02     0.995 0     0.005 0.005                                91     0.98    0.02     0.985 0.01  0.005 0.015                                92     0.98    0.02     0.975 0.005 0.02  0.025                                93     0.98    0.02     0.96  0.02  0.02  0.04                                 94     0.98    0.02     0.95  0.05  0     0.05                                 95     0.98    0.02     0.95  0     0.05  0.05                                 96     0.98    0.02     0.94  0.06  0     0.06                                 97     0.98    0.02     0.94  0     0.06  0.06                                 98     0.97    0.03     1     0     0     0                                    99     0.97    0.03     1.045 0.005 0     0.005                                100    0.97    0.03     1.045 0     0.005 0.005                                101    0.97    0.03     1.025 0.015 0.01  0.025                                102    0.97    0.03     1.01  0.03  0.01  0.04                                 103    0.97    0.03     1     0.03  0.02  0.05                                 104    0.97    0.03     0.99  0.03  0.03  0.06                                 105    0.98    0.02     0.96  0.02  0     0.02                                 106    0.98    0.02     0.98  0.02  0     0.02                                 107    0.98    0.02     1.01  0.02  0     0.02                                 108    0.98    0.02     1.03  0.02  0     0.02                                 109    0.98    0.02     1.05  0.02  0     0.02                                 110    0.99    0.01     0.94  0.01  0.03  0.04                                 111    0.99    0.01     0.96  0.01  0.03  0.04                                 112    0.99    0.01     0.99  0.01  0.03  0.04                                 113    0.99    0.01     1.01  0.01  0.03  0.04                                 114    0.99    0.01     1.03  0.01  0.03  0.04                                 115    0.98    0.02     0.99  0.02  0.01  0.03                                 116    0.98    0.02     0.99  0.02  0.01  0.03                                 117    0.98    0.02     0.99  0.02  0.01  0.03                                 118    0.98    0.02     0.99  0.02  0.01  0.03                                 119    0.98    0.02     0.99  0.02  0.01  0.03                                 120    0.97    0.03     0.99  0.025 0.025 0.05                                 121    0.97    0.03     0.99  0.025 0.025 0.05                                 122    0.97    0.03     0.99  0.025 0.025 0.05                                 123    0.97    0.03     0.99  0.025 0.025 0.05                                 124    0.97    0.03     0.99  0.025 0.025 0.05                                 125    0.97    0.03     0.99  0.025 0.025 0.05                                 126    0.97    0.03     0.99  0.025 0.025 0.05                                 127    0.97    0.03     0.99  0.025 0.025 0.05                                 128    0.97    0.03     0.99  0.025 0.025 0.05                                 129    0.97    0.03     0.99  0.025 0.025 0.05                                 130    0.97    0.03     0.99  0.025 0.025 0.05                                 131    0.97    0.03     0.99  0.025 0.025 0.05                                 132    0.98    0.02     0.99  0.02  0.01  0.03                                 133    0.98    0.02     0.99  0.02  0.01  0.03                                 134    0.98    0.02     0.99  0.02  0.01  0.03                                 135    0.98    0.02     0.99  0.02  0.01  0.03                                 136    0.98    0.02     0.99  0.02  0.01  0.03                                 137    0.98    0.02     0.99  0.02  0.01  0.03                                 138    0.98    0.02     0.99  0.02  0.01  0.03                                 139    0.98    0.02     0.99  0.02  0.01  0.03                                 140    0.98    0.02     0.99  0.02  0.01  0.03                                 141    0.98    0.02     0.99  0.02  0.01  0.03                                 142    0.98    0.02     0.99  0.02  0.01  0.03                                 143    0.98    0.02     0.99  0.02  0.01  0.03                                 144    0.98    0.02     0.99  0.02  0.01  0.03                                 145    0.98    0.02     0.99  0.02  0.01  0.03                                 146    0.98    0.02     0.99  0.02  0.01  0.03                                 147    0.98    0.02     0.99  0.02  0.01  0.03                                 148    0.98    0.02     0.99  0.02  0.01  0.03                                 149    0.98    0.02     0.99  0.02  0.01  0.03                                 150    0.98    0.02     0.99  0.02  0.01  0.03                                 151    0.995   0.005    1     0.03  0.01  0.04                                 152    0.995   0.005    1     0.03  0.01  0.04                                 153    0.995   0.005    1     0.03  0.01  0.04                                 154    0.98    0.005    1     0.03  0.01  0.04                                 155    0.995   0.005    1     0.03  0.01  0.04                                 156    0.995   0.005    1     0.03  0.01  0.04                                 157    0.96    0.04     1.005 0.015 0.01  0.025                                158    0.96    0.04     1.005 0.015 0.01  0.025                                159    0.96    0.04     1.005 0.015 0.01  0.025                                160    0.96    0.04     1.005 0.015 0.01  0.025                                161    0.96    0.04     1.005 0.015 0.01  0.025                                162    0.96    0.04     1.005 0.015 0.01  0.025                                ______________________________________                                    

                                      TABLE 2                                      __________________________________________________________________________     Caramic Compositions                                                           Major Ingredient                                                               Test                                                                              y                                                                           No.                                                                               Sc  Y   Gd  Dy  Ho  Er  Yb  Sum k                                           __________________________________________________________________________     1  0   0   0   0       0   0.01                                                                               0.01                                                                               1.02                                        2  0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        3  0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        4  0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        5  0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        6  0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        7  0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        8  0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        9  0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        10 0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        11 0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        12 0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        13 0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        14 0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        15 0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        16 0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        17 0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        18 0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        19 0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        20 0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        21 0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        22 0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        23 0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        24 0.01                                                                               0   0   0   0   0   0   0.01                                                                               1.02                                        25 0.01                                                                               0   0   0   0   0   0   0.01                                                                               1.02                                        26 0.01                                                                               0   0   0   0   0   0   0.01                                                                               1.02                                        27 0   0.01                                                                               0   0   0   0   0   0.01                                                                               1.02                                        28 0   0.01                                                                               0   0   0   0   0   0.01                                                                               1.02                                        29 0   0.01                                                                               0   0   0   0   0   0.01                                                                               1.02                                        30 0   0   0.01                                                                               0   0   0   0   0.01                                                                               1.02                                        31 0   0   0.01                                                                               0   0   0   0   0.01                                                                               1.02                                        32 0   0   0.01                                                                               0   0   0   0   0.01                                                                               1.02                                        33 0   0   0   0.01                                                                               0   0   0   0.01                                                                               1.02                                        34 0   0   0   0.01                                                                               0   0   0   0.01                                                                               1.02                                        35 0   0   0   0.01                                                                               0   0   0   0.01                                                                               1.02                                        36 0   0   0   0   0.01                                                                               0   0   0.01                                                                               1.02                                        37 0   0   0   0   0.01                                                                               0   0   0.01                                                                               1.02                                        38 0   0   0   0   0.01                                                                               0   0   0.01                                                                               1.02                                        39 0   0   0   0   0   0.01                                                                               0   0.01                                                                               1.02                                        40 0   0   0   0   0   0.01                                                                               0   0.01                                                                               1.02                                        41 0   0   0   0   0   0.01                                                                               0   0.01                                                                               1.02                                        42 0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        43 0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        44 0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        45 0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        46 0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        47 0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        48 0   0   0   0.01                                                                               0   0   0   0.01                                                                               1.04                                        49 0   0   0   0.01                                                                               0   0   0   0.01                                                                               1.04                                        50 0   0   0   0.01                                                                               0   0   0   0.01                                                                               1.04                                        51 0   0   0   0.01                                                                               0   0   0   0.01                                                                               1.04                                        52 0   0   0   0.01                                                                               0   0   0   0.01                                                                               1.04                                        53 0   0   0   0.01                                                                               0   0   0   0.01                                                                               1.04                                        54 0   0   0   0   0   0   0   0   1.04                                        55 0   0   0   0   0   0   0.005                                                                              0.005                                                                              1.04                                        56 0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.04                                        57 0   0   0   0   0   0   0.02                                                                               0.02                                                                               1.04                                        58 0   0   0   0   0   0   0.04                                                                               0.04                                                                               1.04                                        59 0   0   0   0   0   0   0.06                                                                               0.06                                                                               1.04                                        60 0.005                                                                              0   0   0   0   0   0   0.005                                                                              1.04                                        61 0.04                                                                               0   0   0   0   0   0   0.04                                                                               1.04                                        62 0.06                                                                               0   0   0   0   0   0   0.06                                                                               1.04                                        63 0   0.005                                                                              0   0   0   0   0   0.005                                                                              1.04                                        64 0   0.04                                                                               0   0   0   0   0   0.04                                                                               1.04                                        65 0   0.06                                                                               0   0   0   0   0   0.06                                                                               1.04                                        66 0   0   0.005                                                                              0   0   0   0   0.005                                                                              1.04                                        67 0   0   0.04                                                                               0   0   0   0   0.04                                                                               1.04                                        68 0   0   0.06                                                                               0   0   0   0   0.06                                                                               1.04                                        69 0   0   0   0.005                                                                              0   0   0   0.005                                                                              1.04                                        70 0   0   0   0.04                                                                               0   0   0   0.04                                                                               1.04                                        71 0   0   0   0.06                                                                               0   0   0   0.06                                                                               1.04                                        72 0   0   0   0   0.005                                                                              0   0   0.005                                                                              1.04                                        73 0   0   0   0   0.04                                                                               0   0   0.04                                                                               1.04                                        74 0   0   0   0   0.06                                                                               0   0   0.06                                                                               1.04                                        75 0   0   0   0   0   0.005                                                                              0   0.005                                                                              1.04                                        76 0   0   0   0   0   0.04                                                                               0   0.04                                                                               1.04                                        77 0   0   0   0   0   0.06                                                                               0   0.06                                                                               1.04                                        78 0   0   0   0   0   0   0.02                                                                               0.02                                                                               1.01                                        79 0   0   0   0   0   0   0.02                                                                               0.02                                                                               1.01                                        80 0   0   0   0   0   0   0.02                                                                               0.02                                                                               1.01                                        81 0   0   0   0   0   0   0.02                                                                               0.02                                                                               1.01                                        82 0   0   0   0   0   0   0.02                                                                               0.02                                                                               1.01                                        83 0   0   0   0.005                                                                              0   0   0   0.005                                                                              1.04                                        84 0   0   0   0.005                                                                              0   0   0   0.005                                                                              1.04                                        85 0   0   0   0.005                                                                              0   0   0   0.005                                                                              1.04                                        86 0   0   0   0.005                                                                              0   0   0   0.005                                                                              1.04                                        87 0   0   0   0.005                                                                              0   0   0   0.005                                                                              1.04                                        88 0   0   0   0   0   0   0.02                                                                               0.02                                                                               1                                           89 0   0   0   0   0   0   0.02                                                                               0.02                                                                               1                                           90 0   0   0   0   0   0   0.02                                                                               0.02                                                                               1                                           91 0   0   0   0   0   0   0.02                                                                               0.02                                                                               1                                           92 0   0   0   0   0   0   0.02                                                                               0.02                                                                               1                                           93 0   0   0   0   0   0   0.02                                                                               0.02                                                                               1                                           94 0   0   0   0   0   0   0.02                                                                               0.02                                                                               1                                           95 0   0   0   0   0   0   0.02                                                                               0.02                                                                               1                                           96 0   0   0   0   0   0   0.02                                                                               0.02                                                                               1                                           97 0   0   0   0   0   0   0.02                                                                               0.02                                                                               1                                           98 0   0   0   0.04                                                                               0   0   0   0.04                                                                               1                                           99 0   0   0   0.04                                                                               0   0   0   0.04                                                                               1.05                                        100                                                                               0   0   0   0.04                                                                               0   0   0   0.04                                                                               1.05                                        101                                                                               0   0   0   0.04                                                                               0   0   0   0.04                                                                               1.05                                        102                                                                               0   0   0   0.04                                                                               0   0   0   0.04                                                                               1.05                                        103                                                                               0   0   0   0.04                                                                               0   0   0   0.04                                                                               1.05                                        104                                                                               0   0   0   0.04                                                                               0   0   0   0.04                                                                               1.05                                        105                                                                               0   0   0   0   0   0   0.005                                                                              0.005                                                                              0.98                                        106                                                                               0   0   0   0   0   0   0.005                                                                              0.005                                                                              1                                           107                                                                               0   0   0   0   0   0   0.005                                                                              0.005                                                                              1.03                                        108                                                                               0   0   0   0   0   0   0.005                                                                              0.005                                                                              1.05                                        109                                                                               0   0   0   0   0   0   0.005                                                                              0.005                                                                              1.07                                        110                                                                               0   0   0   0.02                                                                               0   0   0   0.02                                                                               0.98                                        111                                                                               0   0   0   0.02                                                                               0   0   0   0.02                                                                               1                                           112                                                                               0   0   0   0.02                                                                               0   0   0   0.02                                                                               1.03                                        113                                                                               0   0   0   0.02                                                                               0   0   0   0.02                                                                               1.05                                        114                                                                               0   0   0   0.02                                                                               0   0   0   0.02                                                                               1.07                                        115                                                                               0   0   0   0.001                                                                              0   0   0.001                                                                              0.002                                                                              1.02                                        116                                                                               0   0   0   0.005                                                                              0   0   0.005                                                                              0.01                                                                               1.02                                        117                                                                               0   0   0   0.01                                                                               0   0   0.01                                                                               0.02                                                                               1.02                                        118                                                                               0   0   0   0.02                                                                               0   0   0.02                                                                               0.04                                                                               1.02                                        119                                                                               0   0   0   0.03                                                                               0   0   0.03                                                                               0.06                                                                               1.02                                        120                                                                               0   0   0   0.03                                                                               0   0   0.01                                                                               0.04                                                                               1.04                                        121                                                                               0   0.01                                                                               0   0   0   0   0.01                                                                               0.02                                                                               1.04                                        122                                                                               0.01                                                                               0   0   0   0.01                                                                               0   0   0.02                                                                               1.04                                        123                                                                               0   0.02                                                                               0   0.02                                                                               0   0   0   0.04                                                                               1.04                                        124                                                                               0   0   0   0   0   0.03                                                                               0.01                                                                               0.04                                                                               1.04                                        125                                                                               0   0.01                                                                               0   0.01                                                                               0   0   0.01                                                                               0.03                                                                               1.04                                        126                                                                               0.01                                                                               0   0   0.02                                                                               0   0   0.01                                                                               0.04                                                                               1.04                                        127                                                                               0   0.01                                                                               0   0.01                                                                               0.01                                                                               0.01                                                                               0   0.04                                                                               1.04                                        128                                                                               0.01                                                                               0.01                                                                               0   0.01                                                                               0   0   0.01                                                                               0.04                                                                               1.04                                        129                                                                               0.005                                                                              0.002                                                                              0.003                                                                              0.005                                                                              0   0.005                                                                              0.005                                                                              0.025                                                                              1.04                                        130                                                                               0.003                                                                              0.005                                                                              0.002                                                                              0.005                                                                              0.005                                                                              0.005                                                                              0.005                                                                              0.03                                                                               1.04                                        131                                                                               0.01                                                                               0.01                                                                               0.005                                                                              0.01                                                                               0.01                                                                               0.01                                                                               0.01                                                                               0.065                                                                              1.04                                        132                                                                               0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        133                                                                               0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        134                                                                               0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        135                                                                               0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        136                                                                               0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        137                                                                               0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        138                                                                               0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        139                                                                               0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        140                                                                               0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        141                                                                               0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        142                                                                               0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        143                                                                               0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        144                                                                               0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        145                                                                               0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        146                                                                               0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        147                                                                               0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        148                                                                               0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        149                                                                               0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        150                                                                               0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.02                                        151                                                                               0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.04                                        152                                                                               0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.04                                        153                                                                               0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.04                                        154                                                                               0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.04                                        155                                                                               0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.04                                        156                                                                               0   0   0   0   0   0   0.01                                                                               0.01                                                                               1.04                                        157                                                                               0   0   0   0.01                                                                               0   0   0   0.01                                                                               1.03                                        158                                                                               0   0   0   0.01                                                                               0   0   0   0.01                                                                               1.03                                        159                                                                               0   0   0   0.01                                                                               0   0   0   0.01                                                                               1.03                                        160                                                                               0   0   0   0.01                                                                               0   0   0   0.01                                                                               1.03                                        161                                                                               0   0   0   0.01                                                                               0   0   0   0.01                                                                               1.03                                        162                                                                               0   0   0   0.01                                                                               0   0   0   0.01                                                                               1.03                                        __________________________________________________________________________

                                      TABLE 3                                      __________________________________________________________________________     Ceramic Compositions                                                           Additive Ingredient                                                                     Composition                                                           Test                                                                              Proportion                                                                           (Mole %)    MO (mole %)                                               No.                                                                               (wt. parts)                                                                          B.sub.2 O.sub.3                                                                   Li.sub.2 O                                                                        SiO.sub.2                                                                         MO BaO                                                                               SrO CaO                                                                               MgO                                                                               ZnO                                          __________________________________________________________________________      1 2     --  1 80 19 20 0   50 30 0                                             2 2     --  1 39 60 20 0   50 30 0                                             3 2     -- 30 30 40 20 0   50 30 0                                             4 2     -- 50 50  0  0 0    0  0 0                                             5 2     -- 20 80  0  0 0    0  0 0                                             6 2     -- 10 50 40 20 0   50 30 0                                             7 2     -- 30 40 30 20 0   50 30 0                                             8 2     -- 20 60 20 20 0   50 30 0                                             9 2     -- 35 65  0  0 0    0  0 0                                            10 2     --  1 59 40 20 0   50 30 0                                            11 2     --  1 85 14 20 0   50 30 0                                            12 2     -- 20 29 51 20 0   50 30 0                                            13 2     -- 50 30 20 20 0   50 30 0                                            14 2     -- 60 30 10 20 0   50 30 0                                            15 2     -- 60 40  0  0 0    0  0 0                                            16 2     -- 10 90  0  0 0    0  0 0                                            17 2     -- 20 60 20 100                                                                               0    0  0 0                                            18 2     -- 20 60 20  0 100  0  0 0                                            19 2     -- 20 60 20  0 0   100                                                                                0 0                                            20 2     -- 20 60 20  0 0    0 100                                                                               0                                            21 2     -- 20 60 20  0 0    0  0 100                                          22 2     -- 20 60 20 20 20  20 20 20                                           23 2     -- 20 60 20 40 10  20 10 20                                           24 2     -- 10 50 40 40 20   0 50 30                                           25 2     -- 20 60 20 20 20   0 50 30                                           26 2     -- 35 65  0  0 0    0  0 0                                            27 2     -- 10 50 40 40 20   0 50 30                                           28 2     -- 20 60 20 20 20   0 50 30                                           29 2     -- 35 65  0  0 0    0  0 0                                            30 2     -- 10 50 40 40 20   0 50 30                                           31 2     -- 20 60 20 20 20   0 50 30                                           32 2     -- 35 65  0  0 0    0  0 0                                            33 2     -- 10 50 40 40 20   0 50 30                                           34 2     -- 20 60 20 20 20   0 50 30                                           35 2     -- 35 65  0  0 0    0  0 0                                            36 2     -- 10 50 40 40 20   0 50 30                                           37 2     -- 20 60 20 20 20   0 50 30                                           38 2     -- 35 65  0  0 0    0  0 0                                            39 2     -- 10 50 40 40 20   0 50 30                                           40 2     -- 20 60 20 20 20   0 50 30                                           41 2     -- 35 65  0  0 0    0  0 0                                            42 0     --  0  0  0  0 0    0  0 0                                            43 0.2   -- 15 75 10 30 10  10 30 20                                           44 1     -- 15 75 10 30 10  10 30 20                                           45 3     -- 15 75 10 30 10  10 30 20                                           46 5     -- 15 75 10 30 10  10 30 20                                           47 7     -- 15 75 10 30 10  10 30 20                                           48 0     --  0  0 100                                                                                0 0    0  0 0                                            49 0.2   -- 15 40 45 20 20  20 20 20                                           50 1     -- 15 40 45 20 20  20 20 20                                           51 3     -- 15 40 45 20 20  20 20 20                                           52 5     -- 15 40 45 20 20  20 20 20                                           53 7     -- 15 40 45 20 20  20 20 20                                           54 1     -- 30 40 30  0 0    0 100                                                                               0                                            55 1     -- 30 40 30  0 0    0 100                                                                               0                                            56 1     -- 30 40 30  0 0    0 100                                                                               0                                            57 1     -- 30 40 30  0 0    0 100                                                                               0                                            58 1     -- 30 40 30  0 0    0 100                                                                               0                                            59 1     -- 30 40 30  0 0    0 100                                                                               0                                            60 1     -- 30 40 30  0 0    0 100                                                                               0                                            61 1     -- 30 40 30  0 0    0 100                                                                               0                                            62 1     -- 30 40 30  0 0    0 100                                                                               0                                            63 1     -- 30 40 30  0 0    0 100                                                                               0                                            64 1     -- 30 40 30  0 0    0 100                                                                               0                                            65 1     -- 30 40 30  0 0    0 100                                                                               0                                            66 1     -- 30 40 30  0 0    0 100                                                                               0                                            67 1     -- 30 40 30  0 0    0 100                                                                               0                                            68 1     -- 30 40 30  0 0    0 100                                                                               0                                            69 1     -- 30 40 30  0 0    0 100                                                                               0                                            70 1     -- 30 40 30  0 0    0 100                                                                               0                                            71 1     -- 30 40 30  0 0    0 100                                                                               0                                            72 1     -- 30 40 30  0 0    0 100                                                                               0                                            73 1     -- 30 40 30  0 0    0 100                                                                               0                                            74 1     -- 30 40 30  0 0    0 100                                                                               0                                            75 1     -- 30 40 30  0 0    0 100                                                                               0                                            76 1     -- 30 40 30  0 0    0 100                                                                               0                                            77 1     -- 30 40 30  0 0    0 100                                                                               0                                            78 3     -- 10 50 40 20 20  20 20 20                                           79 3     -- 10 50 40 20 20  20 20 20                                           80 3     -- 10 50 40 20 20  20 20 20                                           81 3     -- 10 50 40 20 20  20 20 20                                           82 3     -- 10 50 40 20 20  20 20 20                                           83 1     -- 20 60 20  0 100  0  0 0                                            84 1     -- 20 60 20  0 100  0  0 0                                            85 1     -- 20 60 20  0 100  0  0 0                                            86 1     -- 20 60 20  0 100  0  0 0                                            87 1     -- 20 60 20  0 100  0  0 0                                            88 0.5   -- 30 40 30  0 0    0 100                                                                               0                                            89 0.5   -- 30 40 30  0 0    0 100                                                                               0                                            90 0.5   -- 30 40 30  0 0    0 100                                                                               0                                            91 0.5   -- 30 40 30  0 0    0 100                                                                               0                                            92 0.5   -- 30 40 30  0 0    0 100                                                                               0                                            93 0.5   -- 30 40 30  0 0    0 100                                                                               0                                            94 0.5   -- 30 40 30  0 0    0 100                                                                               0                                            95 0.5   -- 30 40 30  0 0    0 100                                                                               0                                            96 0.5   -- 30 40 30  0 0    0 100                                                                               0                                            97 0.5   -- 30 40 30  0 0    0 100                                                                               0                                            98 0.5   -- 30 40 30  0 0    0 100                                                                               0                                            99 3     -- 35 55 10 100                                                                               0    0  0 0                                            100                                                                               3     -- 35 55  3 100                                                                               0    0  0 0                                            101                                                                               3     -- 35 55  3 100                                                                               0    0  0 0                                            102                                                                               3     -- 35 55  3 100                                                                               0    0  0 0                                            103                                                                               3     -- 35 55   3                                                                               100                                                                               0    0  0 0                                            104                                                                               3     -- 35 55  3 100                                                                               0    0  0 0                                            105                                                                               1     -- 10 50 40 20 20  20 20 20                                           106                                                                               1     -- 10 50 40 20 20  20 20 20                                           107                                                                               1     -- 10 50 40 20 20  20 20 20                                           108                                                                               1     -- 10 50 40 20 20  20 20 20                                           109                                                                               1     -- 10 50 40 20 20  20 20 20                                           110                                                                               2     -- 15 75 10  0 0   100                                                                                0 0                                            111                                                                               2     -- 15 75 10  0 0   100                                                                                0 0                                            112                                                                               2     -- 15 75 10  0 0   100                                                                                0 0                                            113                                                                               2     -- 15 75 10  0 0   100                                                                                0 0                                            114                                                                               2     -- 15 75 10  0 0   100                                                                                0 0                                            115                                                                               0.5   -- 30 55 15 20 20  20 20 20                                           116                                                                               0.5   -- 30 55 15 20 20  20 20 20                                           117                                                                               0.5   -- 30 55 15 20 20  20 20 20                                           118                                                                               0.5   -- 30 55 15 20 20  20 20 20                                           119                                                                               0.5   -- 30 55 15 20 20  20 20 20                                           120                                                                               5     -- 35 40 25 20 0   30 50 0                                            121                                                                               5     -- 35 40 25 20 0   30 50 0                                            122                                                                               5     -- 35 40 25 20 0   30 50 0                                            123                                                                               5     -- 35 40 25 20 0   30 50 0                                            124                                                                               5     -- 35 40 25 20 0   30 50 0                                            125                                                                               5     -- 35 40 25 20 0   30 50 0                                            126                                                                               5     -- 35 40 25 20 0   30 50 0                                            127                                                                               5     -- 35 40 25 20 0   30 50 0                                            128                                                                               5     -- 35 40 25 20 0   30 50 0                                            129                                                                               5     -- 35 40 25 20 0   30 50 0                                            130                                                                               5     -- 35 40 25 20 0   30 50 0                                            131                                                                               5     -- 35 40 25 20 0   30 50 0                                            132                                                                               2      1 -- 80 19 20 0   50 30 0                                            133                                                                               2      1 -- 39 60 20 0   50 30 0                                            134                                                                               2     30 --  0 70 20 0   50 30 0                                            135                                                                               2     90 --  0 10 20 0   50 30 0                                            136                                                                               2     90 -- 10  0  0 0    0  0 0                                            137                                                                               2     20 -- 80  0  0 0    0  0 0                                            138                                                                               2     15 -- 30 55 20 0   50 30 0                                            139                                                                               2     45 -- 15 40 20 0   50 30 0                                            140                                                                               2     20 -- 50 30 20 0   50 30 0                                            141                                                                               2     50 -- 30 20 20 0   50 30 0                                            142                                                                               2     10 -- 20 70 20 0   50 30 0                                            143                                                                               2     95 --  5  0  0 0    0  0 0                                            144                                                                               2     10 -- 85  5 20 0   50 30 0                                            145                                                                               2     20 -- 50 30 100                                                                               0    0  0 0                                            146                                                                               2     20 -- 50 30  0 100  0  0 0                                            147                                                                               2     20 -- 50 30  0 0   100                                                                                0 0                                            148                                                                               2     20 -- 50 30  0 0    0 100                                                                               0                                            149                                                                               2     20 -- 50 30  0 0    0  0 100                                          150                                                                               2     20 -- 50 30 20 20  20 20 20                                           151                                                                               0      0 --  0  0  0 0    0  0 0                                            152                                                                               0.2   15 -- 75 10  0 50   0 50 30                                           153                                                                               1     15 -- 75 10  0 50   0 50 30                                           154                                                                               3     15 -- 75 10  0 50   0 50 30                                           155                                                                               5     15 -- 75 10  0 50   0 50 30                                           156                                                                               7     15 -- 75 10  0 50   0 50 30                                           157                                                                               0      0 --  0  0  0 0    0  0 0                                            158                                                                               0.2   45 -- 15 40 20 20  20 20 20                                           159                                                                               1     45 -- 15 40 20 20  20 20 20                                           160                                                                               3     45 -- 15 40 20 20  20 20 20                                           161                                                                               5     45 -- 15 40 20 20  20 20 20                                           162                                                                               7     45 -- 15 40 20 20  20 20 20                                           __________________________________________________________________________

According to Tables 1 and 2, the major ingredient of the dielectric bodies of the capacitors of Test No. 1 was:

    0.98{(Ba.sub.0.98 M.sub.0.04)O.sub.1.02 (Ti.sub.0.99 R.sub.0.01)O.sub.1.995 }+0.02CaZrO.sub.3

or, more specifically, since M₀.04 =Ca₀.03, Sr₀.01, and R₀.01 =Yb₀.01,

    0.98{(Ba.sub.0.98 Ca.sub.0.03 Sr.sub.0.01)O.sub.1.02 (Ti.sub.0.99 Yb.sub.0.01)O.sub.1.995 }+0.02CaZrO.sub.3

One hundred parts by weight of this major ingredient was admixed with 2.0 parts by weight of a additive mixture of one mole percent Li₂ O, 80 mole percent SiO₂ and 19 mole percent MO. The MO was a mixture of 20 mole percent BaO, 50 mole percent CaO, and 30 mole percent MgO.

For the fabrication of the capacitors of Test No. 1 was started with the preparation of the first component, (Ba₀.98 Ca₀.03 Sr₀.01)O₁.02 (Ti₀.99 Yb₀.01)O₁.995, of the major ingredient. We prepared the following start materials for the first component of the major ingredient:

Barium carbonate (BaCO₃): 1065.75 grams (0.98 mole part)

Calcium oxide (CaO): 9.27 grams (0.03 mole part)

Strontium oxide (SrO) 5.71 grams (0.01 mole part)

Titanium oxide (TiO₂): 435.94 grams (0.99 mole part)

Yttrebium oxide (Yb₂ O₃) 10.84 grams (0.005 mole part)

These start materials had all purities of not less than 99.0 percent. The above specified weights of the start materials do not include those of the impurities contained.

We charged the start materials into a pot mill together with alumina balls and 2.5 liters of water and intimately intermingled them by stirring the pot mill for 15 hours. Then we introduced the mixture into a stainless steel pot and dried it by air heated to 150 degrees C. for four hours. Then we crushed the dried mixture into relatively coarse particles and then fired the particles in air within a tunnel furnace at 1200 degrees C. for two hours. There was thus obtained the first component of the major ingredient in finely divided form.

Then we proceeded to the preparation of the second component, CaZrO₃, of the major ingredient of Tset No. 1. We intermingled 448.96 grams of calcium carbonate (CaCO₃) and 551.04 grams at zirconium oxide (ZrO₂). Then we dried and pulverized the mixture and fired the resulting particles in air at 1250 degrees C. for two hours.

Then, in order to obtain the major ingredient of Test No. 1 in the required molar ratio (0.98:0.02) of the first and second components, we intermingled 984.34 grams (98 mole parts) of (Ba₀.98 Ca₀.03 Sr₀.01)O₁.02 (Ti₀.99 Yb₀.01)O₁.995 and 15.66 grams (two mole parts) of CaZrO₃. One thousand grams of the major ingredient was thus obtained in finely divided form.

Then, in order to obtain the additive ingredients of Test No. 1 we first prepared the following substances in the following amounts:

    ______________________________________                                         Li.sub.2 O    0.44   grams (1.0 mole part)                                     SiO.sub.2     70.99  grams (80.0 mole parts)                                   BaCO.sub.3    11.10  grams (3.8 mole parts)                                    CaCO.sub.3    14.70  grams (9.5 mole parts)                                    MgO           3.40   grams (5.7 mole parts)                                    ______________________________________                                    

To these substances we added 300 cubic centimeters of alcohol and stirred the resulting slurry for 10 hours in a polyethylene pot with alumina balls. Then we air fired the mixture at 1000 degrees C. for two hours. Then we charged the fired mixture into an alumina pot together with 300 cubic centimeters of water and pulverized it with alumina balls over a period of 15 hours. Then we dried the pulverized mixture at 150 degrees C. for four hours.

Thus we obtained in finely divided form the desired additive mixture of one mole percent Li₂ O, 80 mole percent SiO₂ and 19 mole percent MO, with the MO consisting of 3.8 mole percent BaO, 9.5 mole percent CaO, and 5.7 mole percent MgO. The relative proportions of BaO, CaO, and MgO were 20, 50 and 30 mole percent.

Then, we added 20 grams (two weight parts) of the second additive ingredient to 1000 grams (100 weight parts) of the major ingredient. Further, to this mixture, we added 15 percent by weight of an organic binder and 50 percent by weight of water with respect to the total weight of the major ingredient and additives. The organic binder was an aqueous solution of acrylic ester polymer, glycerine, and condensed phosphate. Then we ball milled the mixture into a slurry and then defoamed it in vacuum.

Then we charged the defoamed slurry into a reverse roll coater and shaped it into a thin, continuous strip on an elongate backing strip of polyester film. Then we dried the strip by heating it to 100 degrees C. on the backing film. There was thus obtained a green ceramic strip with a thickness of approximately 25 micrometers. We subsequently punched it into "squares" sized 10 by 10 centimeters. These green ceramic squares were to become the ceramic layers 12, FIG. 1, in the completed test capacitors 10.

For the fabrication of the base metal film electrodes 14 on the ceramic layers 12, we prepared 10 grams of nickel in finely divided form, with an average particle size of 1.5 micrometers, and a solution of 0.9 grams of ethyl cellulose in 9.1 grams of butyl "Carbitol" (trademark for diethylene glycol monobutyl ether). We intimately intermingled them in an agitator for 10 hours, thereby providing an electroconductive paste. Then we "printed" the paste on one surface of each green ceramic square, which had been prepared as above stated, through a screen having an array of 50 perforations of rectangular shape, each sized seven by 14 millimeters.

After having allowed the printed paste to dry, we stacked two green squares, with the printings thereon directed upwardly, and with the printings on the two squares offset from each other to an extent approximately half the pitch of the paste pattern in the longitudinal direction. Then we placed the stack of two printed squares between two separate stacks of four unprinted squares each with a thickness of 60 micrometers. Then we exerted a pressure of 39.2 MPa on the resulting stack of printed and unprinted squares in their thickness direction at 50 degrees C., thereby firmly bonding them together. Then we cut the bonded squares in a latticed pattern into 50 laminate chips of identical construction.

We employed a furnace capable of atmosphere control for cofiring the above prepared green dielectric bodies and, buried therein, the conductive layers which were to become the film electrodes 14 in the completed capacitors 10. We first air heated the chips to 600 degrees C. at a rate of 100 degrees C. per hour, thereby driving off the organic binder that had been used for providing the slurry of the powdered major ingredient and additives. Then we changed the furnace atomsphere from air to a reductive (nonoxidative) atmosphere consisting of two percent by volume of molecular hydroge and 98 percent by volume of molecular nitrogen. Then, in this furnace atmosphere, we raised the furnace temperature from 600 degrees C. to 1140 degrees C. at a rate of 100 degrees C. per hour. We maintained for three hours the maximum furnace temperature of 1140 degrees C., at which the ceramic bodies formulated an accordance with our invention were to be sintered to maturity. Then we lowered the furnace temperataure to 600 degrees C. at a rate of 100 degrees C. per hour. Then, with the furnace atmosphere again changed to air (oxidative atmosphere), we maintained the temperature of 600 degrees C. for 30 minutes for the oxidizing heat treatment of the sintered chips. Then we allowed the furnace temperature to drop to room temperature.

Thus we obtained the dielectric ceramic bodies 15 cosintered with the film electrodes 14 buried therein.

We proceeded to the production of the pair of conductive terminations 16 on both sides of each ceramic body 15 at which were exposed the film electrodes 14. First, for the production of the inmost zinc layers 18, we coated both sides of each ceramic body 15 with an electroconductive paste composed of zinc, glass frit and vehicle. Then, after having allowed the coatings to dry, we heated them to 550 degrees C. in air and held the temperature for 15 minutes, thereby completing the zinc layers 18 each in direct contact with one of the two film electrodes 14. Then we formed the intermediate copper layers 20 over the zinc layers 18 by electroless plating, and then the outermost solder layers 22 over the copper layers 20 by electroplating an alloy of lead and tin.

We have thus completed the fabrication of the monolithic, multilayered ceramic test capacitors 10, each constructed as in FIG. 1, in accordance with the ceramic composition of Test No. 1 of Tables 1, 2 and 3. The composition of the ceramic bodies 15 of the thus completed capacitors 10 proved substantially akin to that before sintering.

As for the other ceramic compositions of Tables 1, 2 and 3 designated Tests Nos. 2-162, we made similar capacitors through the same procedure as set forth in the foregoing in connection with the Test No. 1 composition, except for the temperature of sintering in the reductive atmosphere, to which we will presently refer in more detail.

Then we tested all the capacitors of Tests Nos. 1-162 as to their specific dielectric constants, dielectric losses, resistivities, and capacitance-temperature characteristics. We measured these electrical properties of the test capacitors by the following methods:

Specific Dielectric Constant

The capacitance of each test capacitor was first measured at a temperature of 20 degrees C., a frequency of one kilohertz, and an effective voltage of 1.0 volt. Then the specific dielectric constant was computed from the measured value of capacitance, and the area (25 square millimeters) of each of the opposed parts of the film electrodes 14, and the thickness (0.02 millimeter) of that ceramic layer 12 which intervenes between the film electrodes.

Dielectric Loss

The dielectric loss was measured under the same conditions as the specific constant.

Resistivity

Resistance between the pair of conductive terminations 16 of each test capacitor was measured after the application of a direct voltage of 100 volts for one minute. Then the resistivity was computed from the measured resistance value and the size of each test capacitor.

Temperature Dependence of Capacitance

The test capacitors were introduced into a thermostatic oven, and their capacitances at various preselected temperatures were measured at a frequency of one kilohertz and an effective voltage of 1.0 volt. Then the percent changes of the capacitances at -55 degrees and +125 degrees C. from those at 25 degrees C., and at -25 degrees and +85 degrees C. from those at 20 degrees C., were computed.

Table 4 gives the properties of the test capacitors as measured by the above described methods, as well as the maximum temperatures at which the test capacitors were sintered in the reductive atmosphere during their manufacture.

                                      TABLE 4                                      __________________________________________________________________________     Firing Temperature & Capacitor Characteristics                                        Capacitor Characteristics                                                  Firing                                                                             Specific                                                                             Dielectric                                                        Test                                                                              Temp.                                                                              Dielectric                                                                           Loss  Resistivity                                                                            Capacitance Variations (%)                          No.                                                                               (°C.)                                                                       Constant                                                                             (%)   (megohm-cm)                                                                            At -55° C.                                                                    At 125° C.                                                                    At -25° C.                                                                    At 85° C.                  __________________________________________________________________________      1 1140                                                                               3920  1.1   6.7 × 10.sup.6                                                                   -9.8  3.2   -5.5  -6.1                               2 1160                                                                               3880  1.0   8.0 × 10.sup.6                                                                   -9.6  1.3   -4.0  -7.4                               3 1150                                                                               3890  1.2   5.5 × 10.sup.6                                                                   -9.5  4.3   -5.1  -5.2                               4 1140                                                                               3960  1.3   4.2 × 10.sup.6                                                                   -11.0 5.0   -6.0  -5.0                               5 1150                                                                               3860  1.4   4.6 × 10.sup.6                                                                   -11.2 5.7   -6.4  -4.1                               6 1140                                                                               3930  1.3   5.8 × 10.sup.6                                                                   -9.7  2.7   -5.8  -5.7                               7 1140                                                                               3930  1.2   3.9 × 10.sup.6                                                                   -9.9  3.9   -5.7  -6.2                               8 1120                                                                               3910  1.1   5.6 × 10.sup.6                                                                   -11.2 5.1   -5.8  -5.2                               9 1150                                                                               3960  1.2   3.9 × 10.sup.6                                                                   -12.3 5.1   -6.4  -3.9                              10 1150                                                                               3840  1.1   4.5 × 10.sup.6                                                                   -10.3 3.4   -5.8  -6.2                              11 1250                                                                               Not coherently bonded on firing                                         12 1250                                                                               "                                                                       13 1250                                                                               "                                                                       14 1250                                                                               "                                                                       15 1250                                                                               "                                                                       16 1250                                                                               "                                                                       17 1140                                                                               3880  1.2   5.4 × 10.sup.6                                                                   -11.4 4.9   -6.2  -5.1                              18 1150                                                                               3880  1.0   4.4 × 10.sup.6                                                                   -10.5 3.3   -6.6  -5.4                              19 1130                                                                               3920  1.1   6.2 × 10.sup.6                                                                   -10.1 4.9   -5.8  -5.2                              20 1130                                                                               3910  1.2   6.5 × 10.sup.6                                                                   -10.4 4.6   -6.2  -5.2                              21 1140                                                                               3870  1.2   5.1 × 10.sup.6                                                                   -10.8 3.6   -6.1  -5.5                              22 1150                                                                               3910  1.1   5.6 × 10.sup.6                                                                   -11.2 5.0   -6.2  -5.2                              23 1130                                                                               3860  1.3   5.6 × 10.sup.6                                                                   -11.1 4.7   -6.1  -5.3                              24 1130                                                                               3930  1.1   6.1 × 10.sup.6                                                                   -9.8  3.1   -5.4  -6.6                              25 1140                                                                               3920  1.3   4.1 × 10.sup.6                                                                   -8.7  4.0   -6.2  -5.3                              26 1140                                                                               3920  1.2   7.8 × 10.sup.6                                                                   -9.3  5.1   -4.0  -6.3                              27 1150                                                                               3890  1.1   6.1 × 10.sup.6                                                                   -9.7  2.9   -5.5  -4.6                              28 1150                                                                               3880  1.2   3.6 × 10.sup.6                                                                   -10.8 1.8   -5.0  -5.1                              29 1130                                                                               3880  1.2   5.3 × 10.sup.6                                                                   -9.8  4.3   -6.3  -6.1                              30 1140                                                                               3890  1.1   6.2 × 10.sup.6                                                                   -9.6  2.8   -5.5  -5.0                              31 1140                                                                               3890  1.1   4.5 × 10.sup.6                                                                   -9.6  1.5   -5.5  -5.7                              32 1130                                                                               3930  1.2   5.3 × 10.sup.6                                                                   -9.2  4.4   -5.7  -6.3                              33 1140                                                                               3940  1.2   6.8 × 10.sup.6                                                                   -10.4 5.5   -4.9  -5.2                              34 1140                                                                               3920  1.2   7.7 × 10.sup.6                                                                   -10.0 2.8   -4.9  -5.3                              35 1140                                                                               3910  1.2   4.9 × 10.sup.6                                                                   -9.8  1.4   -6.2  -4.5                              36 1140                                                                               3850  1.1   6.0 × 10.sup.6                                                                   - 10.3                                                                               3.9   -5.8  -5.1                              37 1140                                                                               3870  1.0   4.5 × 10.sup.6                                                                   -11.5 1.4   -4.2  -5.0                              38 1140                                                                               3890  1.1   4.1 × 10.sup.6                                                                   -9.6  2.8   -5.5  -5.0                              39 1140                                                                               3950  1.1   5.3 × 10.sup.6                                                                   -11.2 1.4   -4.0  -5.3                              40 1140                                                                               3870  1.2   4.4 × 10.sup.6                                                                   -11.4 4.3   -4.1  -4.8                              41 1140                                                                               3890  1.1   5.0 × 10.sup.6                                                                   -10.6 2.8   -4.4  -5.7                              42 1250                                                                               Not coherently bonded on firing                                         43 1190                                                                               4310  1.5   1.7 × 10.sup.6                                                                   -10.5 2.5   -6.0  -4.9                              44 1170                                                                               4130  1.4   3.4 × 10.sup.6                                                                   -10.6 3.1   -5.9  -4.9                              45 1130                                                                               3540  1.2   5.2 × 10.sup.6                                                                   -12.0 -0.2  -6.9  -6.9                              46 1100                                                                               3260  1.7   3.2 × 10.sup.6                                                                   -11.7 -2.6  -8.0  -8.8                              47 1060                                                                               2820  1.8   1.6 × 10.sup.6                                                                   -15.2 -5.0  -9.8  -12.2                             48 1250                                                                               Not coherently bonded on firing                                         49 1190                                                                               4210  1.2   3.4 × 10.sup.6                                                                   -11.9 6.0   -8.4  -2.5                              50 1160                                                                               4110  1.1   5.9 × 10.sup.6                                                                   -11.3 6.8   -8.6  -1.0                              51 1150                                                                               3740  1.4   7.9 × 10.sup.6                                                                   -13.6 4.3   -8.6  -3.7                              52 1100                                                                               3130  1.8   3.3 × 10.sup.6                                                                   -14.1 1.1   -9.7  -6.2                              53 1090                                                                               2850  2.0   1.6 × 10.sup.6                                                                   -18.4 -2.3  -10.1 -7.2                              54 1180                                                                               4040  1.4   1.5 × 10.sup.6                                                                   -10.2 3.3   -5.9  -5.3                              55 1160                                                                               4100  1.3   2.3 × 10.sup.6                                                                   -9.4  2.9   -5.5  -4.4                              56 1120                                                                               4180  1.2   4.0 × 10.sup.6                                                                   -10.0 2.9   -4.2  -4.1                              57 1090                                                                               4270  1.2   5.5 × 10.sup.6                                                                   -7.6  3.4   -5.1  -3.1                              58 1140                                                                               3970  1.3   2.0 × 10.sup.6                                                                   -9.1  3.1   -5.8  -4.2                              59 1250                                                                               Not coherently bonded on firing                                         60 1140                                                                               4160  1.2   2.7 × 10.sup.6                                                                   -10.0 3.0   -5.0  -4.4                              61 1170                                                                               3980  1.2   1.9 × 10.sup.6                                                                   -9.2  3.5   -5.4  -3.8                              62 1250                                                                               Not coherently bonded on firing                                         63 1130                                                                               4060  1.2   3.3 × 10.sup.6                                                                   -8.7  3.0   -4.6  -4.4                              64 1150                                                                               4000  1.3   2.3 × 10.sup.6                                                                   -10.2 3.7   -5.0  -4.4                              65 1250                                                                               Not coherently bonded on firing                                         66 1130                                                                               4050  1.2   2.8 × 10.sup.6                                                                   -9.6  3.4   -4.5  -4.3                              67 1170                                                                               4010  1.3   2.2 × 10.sup.6                                                                   -10.5 3.1   -4.8  -5.4                              68 1250                                                                               Not coherently bonded on firing                                         69 1110                                                                               4090  1.2   4.1 × 10.sup.6                                                                   -8.9  3.1   -4.9  -3.7                              70 1150                                                                               4120  1.1   2.1 × 10.sup.6                                                                   -9.8  3.4   -5.2  -4.2                              71 1250                                                                               Not coherently bonded on firing                                         72 1160                                                                               4080  1.2   2.9 × 10.sup.6                                                                   -8.4   6.8  -4.8  -4.6                              73 1160                                                                               3980  1.2   2.2 × 10.sup.6                                                                   -8.7  6.7   -5.3  -4.7                              74 1250                                                                               Not coherently bonded on firing                                         75 1140                                                                               4080  1.1   3.1 × 10.sup.6                                                                   -9.8  2.0   -5.0  -4.4                              76 1130                                                                               4020  1.2   2.4 × 10.sup.6                                                                   -9.8  3.4   -5.0  -4.0                              77 1250                                                                               Not coherently bonded on firing                                         78 1160                                                                               3860  1.2   7.0 × 10.sup.6                                                                   -21.2 9.6   -11.9 4.1                               79 1130                                                                               3860  1.2   6.1 × 10.sup.6                                                                   -14.5 4.6   -8.6  -2.6                              80 1110                                                                               3900  1.3   7.3 × 10.sup.6                                                                   -12.0 2.6   -2.1  -5.8                              81 1110                                                                               4000  1.2   7.3 × 10.sup.6                                                                   -4.6  -3.4  -2.0  -8.9                              82 1130                                                                               3880  1.2   7.0 × 10.sup.6                                                                   1.3   -8.0  -0.5  -12.8                             83 1190                                                                               4080  1.2   7.3 × 10.sup.6                                                                   -16.5 7.0   -11.8 3.7                               84 1150                                                                               4210  1.2   5.4 × 10.sup.6                                                                   -13.3 3.3   -9.3  -2.5                              85 1170                                                                               4120  1.3   5.3 × 10.sup.6                                                                   -9.2  -1.3  -2.0  -5.1                              86 1160                                                                               4060  1.2   6.2 × 10.sup.6                                                                   -1.9  -7.4  -0.9  -8.1                              87 1150                                                                               4200  1.2   5.1 × 10.sup.6                                                                   4.1   -12.9 0.9   -11.7                             88 1170                                                                               3870  1.8   3.0 × 10.sup.6                                                                   -17.0 7.0   -11.2 -6.1                              89 1160                                                                               4200  1.3   8.2 × 10.sup.6                                                                   -11.5 7.7   -7.7  -5.1                              90 1150                                                                               4230  1.6   4.1 × 10.sup.6                                                                   -12.5 5.1   -8.3  -5.5                              91 1150                                                                               4030  1.1   8.4 × 10.sup.6                                                                   -11.0 4.9   -6.2  -3.9                              92 1150                                                                               4030  1.6   4.3 × 10.sup.6                                                                   -10.6 3.8   -5.9  -5.0                              93 1170                                                                               3890  1.1   7.5 × 10.sup.6                                                                   -11.3 2.6   -5.8  -6.9                              94 1190                                                                               3840  1.1   7.9 × 10.sup.6                                                                   -10.5 1.3   -6.1  -8.4                              95 1180                                                                               3630  1.7   6.7 × 10.sup.6                                                                   -12.9 1.7   -7.4  -8.2                              96 1200                                                                               3830  1.2   9.8 × 10.sup.6                                                                   -10.9 -2.7  -6.1  -11.8                             97 1190                                                                               3540  1.9   2.2 × 10.sup.6                                                                   -13.5 -3.1  -8.1  -11.5                             98 1140                                                                               3680  1.8   1.3 × 10.sup.6                                                                   -16.0 -12.7 -11.7 -6.5                              99 1120                                                                               3420  1.2   1.9 × 10.sup.6                                                                   -12.2 6.0   -8.9  2.4                               100                                                                               1140                                                                               3610  1.7   1.1 × 10.sup.6                                                                   -11.7 4.1   -9.5  4.1                               101                                                                               1140                                                                               3760  1.4   2.7 × 10.sup.6                                                                   -4.0  2.4   -2.0  -7.1                              102                                                                               1160                                                                               3470  1.2   4.1 × 10.sup.6                                                                   -3.9  1.9   -1.4  -8.4                              103                                                                               1180                                                                               3380  1.1   3.6 × 10.sup.6                                                                   -3.5  -2.4  -1.0  -9.6                              104                                                                               1180                                                                               3280  1.2   3.3 × 10.sup.6                                                                   -3.9  -4.3  -1.7  -11.0                             105                                                                               1120                                                                               3170  2.7   5.4 × 10.sup.4                                                                   -19.2 -12.4 -14.9 -8.3                              106                                                                               1140                                                                               3830  1.1   3.3 × 10.sup.6                                                                   -12.6 7.1   -6.8  -4.7                              107                                                                               1170                                                                               3790  1.0   4.2 × 10.sup.6                                                                   -10.0 5.9   -7.0  -4.2                              108                                                                               1190                                                                               3630  1.3   4.9 × 10.sup.6                                                                   -9.5  2.7   -5.9  -5.2                              109                                                                               1250                                                                               Not coherently bonded on firing                                         110                                                                               1120                                                                               3190  3.9   4.7 × 10.sup.4                                                                   -21.3 -10.2 -15.5 -9.2                              111                                                                               1140                                                                               3750  1.3   5.0 × 10.sup.6                                                                   -12.2 5.9   -8.0  -3.5                              112                                                                               1140                                                                               3790  1.1   7.4 × 10.sup.6                                                                   -13.3 2.7   -7.4  -3.8                              113                                                                               1180                                                                               3630  1.3   8.0 × 10.sup.6                                                                   -10.0 1.2   -7.6  -3.5                              114                                                                               1250                                                                               Not coherently bonded on firing                                         115                                                                               1150                                                                               3810  1.1   1.3 × 10.sup.6                                                                   -10.8 -0.9  -5.3  -6.8                              116                                                                               1120                                                                               3960  1.1   4.0 × 10.sup.6                                                                   -9.4  -1.0  -4.9  -6.2                              117                                                                               1130                                                                               4140  1.1   4.8 × 10.sup.6                                                                   -8.9  -0.8  -4.0  -5.6                              118                                                                               1150                                                                               3860  1.0   3.1 × 10.sup.6                                                                   -10.4 -1.1  -5.1  -6.4                              119                                                                               1250                                                                               Not coherently bonded on firing                                         120                                                                               1140                                                                                3840 1.2   4.1 × 10.sup.6                                                                   -3.8  -3.0  -1.0  -7.0                              121                                                                               1120                                                                               4130  1.2   5.5 × 10.sup.6                                                                   -3.8  -2.5  -1.0  -7.3                              122                                                                               1130                                                                               4100  1.2   3.7 × 10.sup.6                                                                   -3.2  -2.2  -1.4  -7.3                              123                                                                               1140                                                                               3870  1.2   3.9 × 10.sup.6                                                                   -3.8  -3.6  -2.0  -8.7                              124                                                                               1150                                                                               3820  1.1   3.4 × 10.sup.6                                                                   -3.9  -3.5  -2.2  -8.3                              125                                                                               1150                                                                               3990  1.1   5.1 × 10.sup.6                                                                   -3.6  -2.9  -1.3  -8.0                              126                                                                               1160                                                                               3860  1.2   2.1 × 10.sup.6                                                                   -4.7  -3.8  -1.9  -8.4                              127                                                                               1160                                                                               3820  1.3   3.1 × 10.sup.6                                                                   -4.5  -3.3  -1.8  -8.1                              128                                                                               1140                                                                               3840  1.1   2.0 × 10.sup.6                                                                   -4.0  -3.7  -1.7  -8.7                              129                                                                               1140                                                                               4160  1.0   2.8 × 10.sup.6                                                                   -3.8  -2.8  -1.6  -7.7                              130                                                                               1150                                                                               3950  1.2   4.5 × 10.sup.6                                                                   -4.1  -3.0  -1.4  - 8.3                             131                                                                               1250                                                                               Not coherently bonded on firing                                         132                                                                               1130                                                                               3690  1.2   5.4 × 10.sup.6                                                                   -11.2 4.1   -7.4  -4.5                              133                                                                               1140                                                                               3660  1.1   4.2 × 10.sup.6                                                                   -9.9  2.9   -4.7  -4.1                              134                                                                               1110                                                                               3630  1.1   3.7 × 10.sup.6                                                                   -9.4  3.5   -4.2  -3.9                              135                                                                               1090                                                                               3550  1.2   3.5 × 10.sup.6                                                                   -12.4 5.9   -4.9  -1.8                              136                                                                               1100                                                                               3610  1.1   4.1 × 10.sup.6                                                                   -10.9 6.4   -7.1  -1.6                              137                                                                               1110                                                                               3680  1.2   2.1 × 10.sup.6                                                                   -9.6  4.4   -5.4  -3.1                              138                                                                               1120                                                                               3780  1.2   3.4 × 10.sup.6                                                                   -11.3 3.1   -4.4  -5.2                              139                                                                               1110                                                                               3690  1.0   4.0 × 10.sup.6                                                                   -11.1 2.5   -6.2  -6.2                              140                                                                               1130                                                                               3650  1.1   3.9 × 10.sup.6                                                                   -10.2 2.9   -6.1  -4.2                              141                                                                               1110                                                                               3690  0.9   3.3 × 10.sup.6                                                                   -11.3 4.4   -5.5  -2.3                              142                                                                               1250                                                                               Not coherently bonded on firing                                         143                                                                               1250                                                                               "                                                                       144                                                                               1250                                                                               "                                                                       145                                                                               1130                                                                               3690  0.9   3.9 × 10.sup.6                                                                   -9.8  4.3   -3.5  -4.7                              146                                                                               1140                                                                               3630  1.1   5.5 × 10.sup.6                                                                   -9.3  1.5   -4.0  -4.6                              147                                                                               1130                                                                               3790  1.2   4.8 × 10.sup.6                                                                   -10.6 1.4   -5.9  -6.5                              148                                                                               1130                                                                               3760  1.1   7.3 × 10.sup.6                                                                   -8.0  1.6   -4.6  -6.7                              149                                                                               1130                                                                               3690  1.2   4.2 × 10.sup.6                                                                   -11.4 4.1   -6.4  -5.9                              150                                                                               1130                                                                               3810  1.2   4.7 × 10.sup.6                                                                   -10.0 3.7   -5.5  -6.4                              151                                                                               1250                                                                               Not coherently bonded on firing                                         152                                                                               1170                                                                               4400  1.4   1.7 × 10.sup.6                                                                   -8.9  2.1   -4.6  -3.6                              153                                                                               1150                                                                               4150  1.0   2.6 × 10.sup.6                                                                   -6.5  3.7   -2.9  -3.9                              154                                                                               1110                                                                               3720  1.0   3.5 × 10.sup.6                                                                   -7.4  -0.8  -2.8  -8.1                              155                                                                               1090                                                                               3420  0.2   2.1 × 10.sup.6                                                                   -9.9  -2.5  -6.7  -8.5                              156                                                                               1050                                                                               2910  1.4   2.1 × 10.sup.6                                                                   -14.4 -6.3  -8.1  -10.7                             157                                                                               1250                                                                               Not coherently bonded on firing                                         158                                                                               1180                                                                               4250  1.4   4.1 × 10.sup.6                                                                   2.3   4.6   -5.8  -0.4                              159                                                                               1150                                                                               3980  1.0   5.0 × 10.sup.6                                                                   -10.1 5.9   -6.0  -0.7                              160                                                                               1110                                                                               3760  1.0   5.3 × 10.sup.6                                                                   -9.5  1.6   -5.7  -3.5                              161                                                                               1070                                                                               3380  1.1   2.8 × 10.sup.6                                                                   -12.1 0.8   -8.4  -6.5                              162                                                                               1040                                                                               2990  1.5   2.9 × 10.sup.6                                                                   -16.8 -5.5  -9.0  -5.7                              __________________________________________________________________________

It will be noted from Table 4 that the specific dielectric constants of the Test No. 1 capacitors, for instance, averaged 3920, their dielectric losses 1.1 percent, their resistivities 6.7×10⁶ megohm-centimeters, and their percent variations of capacitances from those at 25 degrees C. to those at -55 degrees and +125 degrees C., -9.8 and +3.2 percent, and from those at 20 degrees C. to those at -25 degrees and +85 degrees C., -5.5 and -6.1 percent, respectively.

Before proceeding further with the examination of Table 4, we will determine the criteria of acceptability for the four electrical properties in question of the capacitors as follows:

Specific dielectric constant, at least 3000.

Dielectric loss, not more than 2.5 percent.

Resistivity, at least 1×10⁶ megohm-centimeters.

Temperature dependence of capacitance, within plus and minus 15 percent at -55 degrees and +125 degrees C., and within plus and minus 10 percent at -25 degrees and +85 degrees C.

A reconsideration of Table 4 in light of the above established criteria of favorable capacitor characteristics will reveal that the capacitors of Tests Nos. 11-16, 42, 47, 48, 53, 59, 62, 65, 68, 71, 74, 77, 78, 82, 83, 87, 88, 96-98, 104, 105, 109, 110, 114, 119, 131, 142-144, 151, 156, 157 and 162 do not meet these criteria. Accordingly, the corresponding ceramic compositions of Tables 1, 2 and 3 fall outside the scope of our invention. All the other test capacitors come up to these criteria even through they were sintered at temperatures of less than 1200 degrees C. in a reductive atmosphere.

Although Table 4 gives the precent variations of capacitances only at -55 degrees, +125 degrees, -25 degrees and +85 degrees C., we actually measured the capacitances at additional temperatures of 0 degrees, +20 degrees, +25 degrees, +40 degrees, +60 degrees and +105 degrees C. The capacitance variations of all the test capacitors in accordance with our invention were within plus and minus 10 percent in the temperature range of -25 degrees to +85 degrees C. and within plus and minus 15 percent in the temperature range of -55 degrees to +125 degrees C.

Now, let us study the ceramic compositions of Tables 1, 2 and 3, and the corresponding capacitor characteristics of Table 4 in more detail.

As for the major ingredient, (1-α){(Ba_(k-x) M_(x))O_(k) (Ti_(1-y) R_(y))O₂₋(y/2) {+αCaZrO₃, we tested various values for α, k, x, z and y in order to determine desirable ranges of such values. First of all, the value of the x was set at zero in Tests Nos. 88 and 89. In the resulting capacitors the capacitance variation at -25 degrees C. was outside the desired range of plus and minas 10 percent, and the capacitance variation at -55 degrees C. was outside the desired range of plus and minus 15 percent. However, all the desired electrical characteristics were obtained when the value of the x was set at 0.005 as in Tests Nos. 89 and 99. Thus we set the lowest possible value of the x at 0.005.

The tests Nos. 96, 97, and 104 compositions had the value of the x set at 0.06. The capacitance variation of the resulting capacitors at +85 degrees C. fell outside the desired range of plus and minus 10 percent. All the desired electrical characteristics were obtained when the value of the x was set at 0.05 as in Tests Nos. 94, 95 and 103. The highest possible value of the x is therefore 0.05.

The capital M in the formula of the major ingredient represents either or both of Ca and Sr as aforesaid. The Tests indicate that the use of either or both of Ca and Sr does not substantially affect the characteristics of the resulting capacitors, and that the value of X can be in the range of 0.005 to 0.05 in either case.

The Tests Nos. 59, 62, 65, 68, 71, 74 and 77 compositions had the value of y set at 0.06. The dielectric bodies formulated accordingly were not coherently bonded on firing. All the desired electrical characteristics were obtained when the value of y was set at 0.04 as in Tests Nos. 58, 61, 64, 67, 70, 73, and 76. The highest possible value of y is therefor 0.04.

The capital R in the formula of the major ingredient represents at least one rare earth element selected from Sc, Y, Gd, Dy, Ho, Er, Yb, Tb, Tm and Lu as aforesaid. The Tests indicate that the use of one or plural of the rare earth elements does not substantially affect the characteristics of the resulting capacitors, and that the value of y can be in the range zero to 0.04.

The addition of the rare earth elements to the major ingredient improves the temperature dependence of capacitance. The rare earth elements serve to make the capacitors that the capacitance variation is from -15 percent to +15 percent in a temperature range of -55 degrees to +125 degrees C., and form -10 percent to +10 percent in a temperature range of -25 degrees to +85 degrees C. Also, the rare earth elements serve to make the dielectric bodies with a high resistivity. Furthermore, the rare earth elements serve to make the ceramic bodies having higher coherency.

The value of α in the formula of the major ingredient was set at zero in Tests Nos. 78 and 83. The capacitance variations of the resulting capacitors fell outside the desired range of plus and minus 10 percent at -25 degrees C. and the desired range of plus and minus 15 percent at -55 degrees C. All the desired characteristics were met when the value of α was set at 0.005 as in Tests Nos. 79 and 84. The lowest possible value of α is therefore 0.005.

The value 0.05 chosen for α in Tests 82 and 87 was too high because the capacitance variations of the resulting capacitors at 85 degrees C. fell outside the desired range of plus and minus 10 percent. All the desired characteristics were achived when the value of α was set at 0.04 as in Tests Nos. 81 and 86. The highest possible value of α is therefor 0.04.

When the value of K was set at 0.98 as in Test Nos. 105 and 110, the resistivities of the resulting capacitors were both less than 1×10⁶ megohm-centimeters. The capacitor characteristics were all satisfactory when the value of K was set at 1.00 at in Tests Nos. 106, and 111. The lowest possible value of K is therefore 1.00.

When the value of K was set at 1.07 as in Tests Nos. 109 and 114, the resulting dielectric bodies were not coherently bonded on firing. Coherently bonded ceramic bodies were obtained, and the capacitor characteristics were all satisfactory, when the value of K was set at 1.05 as in Tests Nos. 99-103, 108 and 113. The upper limit of the possible values of K is therefore 1.05.

The ceramic compositions of Tests Nos. 42 and 48 contained no the additive ingredient specified by our invention. The dielectric bodies formulated accordingly were not coherently bonded on firing at a temperature as high as 1250 degrees C. For comparision the ceramic compositions of Tests Nos. 43 and 49 contained 0.2 part by weight of the additive ingredient with respect to 100 parts by weight of the major ingredient. Even though the firing temperatures for these test capacitors were as low as 1190 and 1180 degrees C., they possessed the desired electrical characteristics. We set, therefore, the lower limit of the possible proportions of the additive ingredient at 0.2 part by weight with respect to 100 parts by weight of the major ingredient.

The tests Nos. 47 and 53 ceramic compositions contained 7 parts by weight of the additive ingredient with respect to 100 parts by weight of the major ingredient. The specific dielectric constants of the resulting capacitors were less than the above established criterion of 3000. Also, their capacitance variations were outside the range of plus and minus 15 percent at -55 degrees C. However, when the proportion of the additive ingredient was reduced to five parts by weight as in Tests Nos. 46 and 52, the resulting capacitors had all the desired electrical characteristics. Accordingly, the upper limit of the possible proportions of the additive ingredient is set at five parts by weight with respect to 100 parts by weight of the major ingredient.

We have ascertained from the results of the Tests Nos. 1-16 that the acceptable range of the relative proportions of Li₂ O, SiO₂ and MO, the additive ingredient of the ceramic compositions in accordance with our invention, can be definitely stated in reference to the ternary diagram of FIG. 2. The point A in the ternary diagram indicates the Test No. 1 additive composition of one mole percent Li₂ O, 80 mole percent SiO₂, and 19 mole percent MO. The point B indicates the Test No. 2 additive composition of one mole percent Li₂ O, 39 mole percent SiO₂, and 60 mole percent MO. The point C indicates the Test No. 3 additive composition of 30 mole percent Li₂ O, 30 mole percent SiO₂, and 40 mole percent MO. The point D indicates the Test No. 4 additive composition of 50 mole percent Li₂ O, 50 mole percent SiO₂, and 0 mole percent MO. The point E indecates the Test No. 5 additive composition of 20 mole percent Li₂ O, 80 mole percent SiO₂, and 0 mole percent MO.

The relative proportions of the additives Li₂ O, SiO₂, and MO of the ceramic compositions in accordance with our invention are within the region bounded by the lines sequentially connecting the above defined points A, B, C, D and E in the ternary diagram of FIG. 2.

Tables 1, 2, 3 and 4 prove that the additive compositions within the above defined region makes possible the provision of capacitors of the desired characteristics. The additive compositions of Tests Nos. 11-16 all fall outside that region, and the corresponding dielectric bodies were not coherently bonded on firing at a temperature of as high as 1250 degrees C. The above specified acceptable range of the relative proportions of the additives holds true regardless of whether only one of BaO, MgO, ZnO, SrO and CaO is employed as MO, as in Tests Nos. 17-21, or two or more or all of them are employed as in the other Tests.

Also, we have ascertained from the results of the Tests Nos. 132-162 that the acceptable range of the relative proportions of B₂ O₃, SiO₂ and MO, the additive ingredient of the ceramic compositions in accordance with our invention, can be definitely stated in reference to the ternary diagram of FIG. 3. The point A in the ternary diagram indicates the Test No. 132 additive composition of one mole percent B₂ O₃, 80 mole percent SiO₂, and 19 mole percent MO. The point B indicates the Test No. 133 additive composition of one mole percent B₂ O₃, 39 mole percent SiO₂, and 60 mole percent MO. The point C indicates the Test No. 134 additive composition of 30 mole percent B₂ O₃, 0 mole percent SiO₂, and 70 mole percent MO. The point D indicates the Test No. 135 additive composition of 90 mole percent B₂ O₃, 0 mole percent SiO₂ , and 10 mole percent MO. The point E indicates the Test No. 136 additive composition of 90 mole percent B₂ O₃, 10 mole percent SiO₂, and 0 mole percent MO. The point F indicates the Test No. 137 additive composition of 20 mole percent B₂ O₃, 80 mole percent SiO₂, and 0 mole percent MO.

The relative proportions of the additives B₂ O₃, SiO₂ and MO of the ceramic compositions in accordance with our invention are within the region bounded by the lines sequentially connecting the above defined points A, B, C, D, E and F in the ternary diagram of FIG. 3.

Tables 1, 2, 3 and 4 prove that the additive compositions within the above defined region makes possible the provision of capacitors of the desired characteristics. The additive compositions of Tests Nos. 142-144 all fall outside that region, and the corresponding dielectric bodies were not coherently bonded on firing at a temperature of as high as 1250 degrees C. The above specified acceptable range of the relative proportions of the additives holds true regardless of whether only one of BaO, MgO, ZnO, SrO and CaO is employed as MO, as in Tests Nos. 145-149, or two or more or all of them are employed as in the other Tests.

Although we have disclosed our invention in terms of specific Examples thereof, we understand that our invention is not to be limited by the exact details of such disclosure but admits of a variety of modifications or alterations within the usual knowledge of the ceramists, chemists or electricians without departing from the scope of the invention. The following, then, is a brief list of such possible modifications or alterations:

1. The low temperature sinterable ceramic compositions of our invention may contain various additives other than those disclosed herein. An example is a mineralizer such as manganese dioxide. Used in a proportion (preferably from 0.05 to 0.1 percent by weight) not adversely affecting the desired characteristics of the resulting capacitors, the mineralizer will serve to improve the sinterability of the ceramic compositions.

2. The start materials of the ceramic compositions in accordance with our invention may be substances such as oxides or hydroxides other than those employed in the foregoing examples.

3. The temperature of the oxidizing heat treatment need not necessarily be 600 degrees C. but can be variously determined in a range (from 500 degrees to 1000 degrees C. for the best results) not exceeding the temperature of the preceding sintering in a nonoxidative atmosphere, the oxidizing temperature being dependent upon factors such as the particular base metal electrode material in use and the degree of oxidation required for each ceramic material to be produced.

4. The temperature of cosintering in a nonoxidative atmosphere may also be changed in consideration of the particular electrode material in use. We recommend a range of 1050 degrees to 1200 degrees C. if the electrode material is nickel, as we have ascertained by experiment that little or no flocculation of the nickel particles takes place in that temperature range.

5. The dielectric bodies formulated in accordance with our invention, with or without electrodes buried therein or otherwise attached thereto, may be sintered in a neutral, instead of reductive, atmosphere.

6. The principles of our invention may be applied to capacitors other than those of the monolithic, multilayered configuration disclosed herein. 

What we claim is:
 1. A solid dielectric capacitor comprising a dielectric ceramic body and at least two electrodes in contact therewith, the dielectric ceramic body consisting essentially of:(a) 100 parts by weight of a major ingredient expressed by the formula,

    (1-α){(Ba.sub.k-x M.sub.x)O.sub.k (Ti.sub.1-y R.sub.y)O.sub.2-(y/2) }+αCaZrO.sub.3

whereM is either or both of calcium and strontium; R is at least one metal selected from scandium, yttrium, gadolinium, dysprosium, holmium, erbium, ytterbium, terbium, thulium and lutetium; α is a numeral in the range of 0.005 to 0.040; k is a numeral in the range of 1.00 to 1.05; x is a numeral in the range of 0.005 to 0.050; and y is a numeral greater than 0 and not greater than 0.04; and (b) from 0.2 to 5.0 parts by weight of an additive mixture of at least two members selected from the group consisting of boric oxide or lithium oxide, silicon oxide and at least one metal oxide selected form the group consisting of barium oxide, strontium oxide, calcium oxide, magnesium oxide and zinc oxide.
 2. The solid dielectric capacitor of claim 1 wherein the additive mixture is an additive mixture of lithium oxide, silicon dioxide and at least one metal oxide selected from the group consisting of barium oxide, strontium oxide, calcium oxide, magnesium oxide and zinc oxide, the relative proportions of lithium oxide, silicon dioxide and at least one selected metal oxide constituting the additive mixture being in that region of the ternary diagram of FIG. 2 attached hereto which is bounded by lines sequentially connecting:the point A where the additive mixture consists of one mole percent lithium oxide, 80 mole percent silicon dioxide, and 19 mole percent metal oxide; the point B where the additive mixture consists of one mole percent lithium oxide, 39 mole percent silicon dioxide, and 60 mole percent metal oxide; the point C where the additive mixture consists of 30 mole percent lithium oxide, 30 mole percent silicon dioxide, and 40 mole percent metal oxide; the point D where the additive mixture consists of 50 mole percent lithium oxide, 50 mole percent silicon dioxide, and 0 mole percent metal oxide; and the point E where the additive mixture consists of 20 mole percent boric oxide, 80 mole percent silicon dioxide, and 0 mole percent metal oxide.
 3. The solid dielectric capacitor of claim 1 wherein the additive mixture is an additive mixture of boric oxide, silicon dioxide and at least one metal oxide selected from the group consisting of barium oxide, strontium oxide, calcium oxide, magnesium oxide and zinc oxide, the relative proportions of boric oxide, silicon dioxide and at least one selected metal oxide constituting the additive mixture being in that region of the ternary diagram of FIG. 3 attached hereto which is bounded by lines sequentially connecting:the point A where the additive mixture consists of one mole percent boric oxide, 80 mole percent silicon dioxide, and 19 mole percent metal oxide; the point B where the additive mixture consists of one mole percent boric oxide, 39 mole percent silicon dioxide, and 60 mole percent metal oxide; the point C where the additive mixture consists of 30 mole percent boric oxide, 0 mole percent silicon dioxide, and 70 mole percent metal oxide; the point D where the additive mixture consists of 90 mole percent boric oxide, 0 mole percent silicon dioxide, and 10 mole percent metal oxide; the point E where the additive mixture consists of 90 mole percent boric oxide, 10 mole percent silicon dioxide, and 0 mole percent metal oxide; and the point F where the additive mixture consists of 20 mole percent boric oxide, 80 mole percent silicon dioxide, and 0 mole percent metal oxide.
 4. The solid dielectric capacitor of claim 1, 2 or 3 wherein the electrodes are buried in the dielectric ceramic body.
 5. The solid dielectric capacitor of claims 1, 2 or 3 wherein the electrodes are of a base metal.
 6. The solid dielectric capacitor of claim 5 wherein the base metal is nickel.
 7. A process for the manufacture of a solid dielectric capacitor which comprises:(a) providing in finely divided form a mixture of: 100 parts by weight of a major ingredient expressed by the formula,

    (1-α){(Ba.sub.k-x M.sub.x)O.sub.k (Ti.sub.1-y R.sub.y)O.sub.2-(y/2) }+αCaZrO.sub.3

whereM is either or both of calcium and strontium; R is at least one metal selected from scandium, yttrium, gadolinium, dysprosium, holmium, erbium, ytterbium, terbium, thulium and lutetium; α is a numeral in the range of 0.005 to 0.04; k is a numeral in the range of 1.00 to 1.05; x is a numeral in the range of 0.005 to 0.050; and y is a numeral greater than 0 and not greater than 0.04; and from 0.2 to 5.0 parts by weight of an additive mixture of at least two members selected from the group consisting of boric oxide or lithium oxide, silicon oxide and at least one metal oxide selected form the group consiting of barium oxide, strontium oxide, calcium oxide, magnesium oxide and zinc oxide; (b) molding the mixture into desired shape and size, the molding having at least two electrode portions of an electroconductive material; (c) cosintering the molding and the electrode portions to maturity in a nonoxidative atmosphere; and (d) heating the cosintered molding and electrode portions in an oxidative atomsphere.
 8. The process of claim 7 wherein the electrode portions are formed on the molding by coating the same with an electroconductive paste composed principally of a base metal.
 9. The process of claim 8 wherein the base metal is nickel.
 10. The process of claim 7 wherein the molding and the electrode portions are cosintered in a temperature range of 1050 degrees to 1200 degrees C.
 11. The process of claim 7 wherein the cosintered molding and electrode portions are heated in a temperature range of 500 degrees to 1000 degrees C. 